Simultaneous harnessing of hot electrons and hot holes achieved via n-metal-p Janus plasmonic heteronanocrystals

Wan, Xiaohua; Gao, Yulong; Eshete, Mesfin; Hu, Min; Pan, Rongrong; Wang, Hongzhi; Liu, Lizhen; Liu, Jia; Jiang, Jun; Brovelli, Sergio; Zhang, Jiatao

doi:10.1016/j.nanoen.2022.107217

Cited by 33 publications

(28 citation statements)

References 65 publications

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“…The CEf nonepitaxial strategy has shown a wide applicability for construction of various chalcogenide semiconductor shells on plasmonic metal cores featuring well‐defined interfacial properties. [ 87–94,141–154 ] This was established on judicious modulation of the chemical thermodynamics and kinetics of cation exchange reactions which can be simply described by Equation ( ) .

M_{normalm} X + n N^{m +} \overset{solvent or ligand}{9extrue\to} N_{normaln} X + m M^{n +}

where M and N refer to the host cations and guest cations, respectively, and X stands for the anions. Of particular importance, herein, the hard and soft acids and bases (HSAB) theory is a fundamental rule dominating the driving force for cation exchange, primarily by regulation of the interaction strength between cations and the ligand or solvent molecules.…”

Section: Cef Nonepitaxial Growth Of Plasmonic Metal@semiconductor Pho...mentioning

confidence: 99%

“…For example, the first n–metal–p‐type heteronanocrystals that consist of a plasmonic core (Au nanorod) shelled by both n‐type (CdS) and p‐type (PbS) semiconductors in a Janus configuration (termed as Au@(PbS–CdS) core–Janus shell nanostructures, Figure 13L,m) were created, based on sequential partial cation exchange‐mediated nonepitaxial growth, as illustrated in Figure a. [ 153 ] The resulting materials displayed organized interfaces at the M–n, M–p, and p–n junctions (Figure 16b–d), which were essentially inaccessible by other synthetic methods due to the large lattice mismatches. Such interface control avoided the formation of interface defects and promoted the extraction of hot electrons from Au plasmon via the Schottky barrier at Au–CdS interface (Figure 16e).…”

Section: Cef Nonepitaxial Growth Of Plasmonic Metal@semiconductor Pho...mentioning

confidence: 99%

“…The CEf nonepitaxial strategy has shown a wide applicability for construction of various chalcogenide semiconductor shells on plasmonic metal cores featuring well-defined interfacial properties. [87][88][89][90][91][92][93][94][141][142][143][144][145][146][147][148][149][150][151][152][153][154] This was established on judicious modulation of the chemical thermodynamics and kinetics of cation exchange reactions which can be simply described by Equation ( 4).…”

Section: Synthesis and Modulationmentioning

confidence: 99%

“…[91] Aside from the typical core-shell structure, yolkshell, nonconcentric core-shell, and core-Janus shell structures can also be constructed for the plasmonic metal-semiconductor associations. [92,145,147,153] The morphology of the CEf nonepitaxial-yielded metal@semiconductor products can be readily tailored encompassing nanospheres, nanorods (with varied length-todiameter aspect ratios), triangle nanoprisms, nanodumbbells, nanoribbons, etc. [94,144,145,148] Among these manifold heterostructures, elaborate engineering of the metal-semiconductor interface can be fulfilled to acquire atomically clean and organized interfacial structures irrespective of the degree of lattice mismatch.…”

Section: Synthesis and Modulationmentioning

confidence: 99%

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confidence: 99%

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Construction of Plasmonic Metal@Semiconductor Core–Shell Photocatalysts: From Epitaxial to Nonepitaxial Strategies

2022

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Figure 1. a) Schematic illustration of LSPR excitation for spherical Au NPs. b,c) Schematic illustration of LSPR excitation for rod-shaped Au NPs along the (b) transverse and (c) longitudinal direction. d) UV-vis spectra for spherical Au NPs with different particle sizes. Reproduced with permission. [48] Copyright 2007, American Chemical Society. e) Extinction spectra for rod-shaped Au NPs with different length-to-diameter aspect ratios. Reproduced with permission. [27] Copyright 2014, Wiley-VCH.

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M_{normalm} X + n N^{m +} \overset{solvent or ligand}{9extrue\to} N_{normaln} X + m M^{n +}

Section: Cef Nonepitaxial Growth Of Plasmonic Metal@semiconductor Pho...mentioning

confidence: 99%

Section: Cef Nonepitaxial Growth Of Plasmonic Metal@semiconductor Pho...mentioning

confidence: 99%

Section: Synthesis and Modulationmentioning

confidence: 99%

Section: Synthesis and Modulationmentioning

confidence: 99%

mentioning

confidence: 99%

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Construction of Plasmonic Metal@Semiconductor Core–Shell Photocatalysts: From Epitaxial to Nonepitaxial Strategies

2022

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Thermionic Emission in Artificially Structured Single‐Crystalline Elemental Metal/Compound Semiconductor Superlattices

Rawat,

Rao,

Rudra

et al. 2024

Advanced Materials

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Metal/semiconductor superlattices represent a fascinating frontier in materials science and nanotechnology, where alternating layers of metals and semiconductors are precisely engineered at the atomic and nano‐scales. Traditionally, epitaxial metal/semiconductor superlattice growth requires constituent materials from the same family, exhibiting identical structural symmetry and low lattice mismatch. Here, beyond this conventional constraint, a novel class of epitaxial lattice‐matched metal/semiconductor superlattices is introduced that utilizes refractory hexagonal elemental transition metals and wide‐bandgap III‐nitride semiconductors. Exemplified by the Hf/AlN superlattices exhibiting coherent layer‐by‐layer epitaxial growth, cross‐plane thermionic emission is observed through current–voltage measurements accomplished for the first time in any metal/semiconductor superlattices. Further, thermoreflectance measurements reveal significant enhancement in cross‐plane Seebeck coefficients attributed to carrier energy filtering by Schottky barriers. Demonstration of artificially structured elemental‐metal/wide‐bandgap compound‐semiconductor superlattices promises to usher in new fundamental physics studies and cutting‐edge applications such as tunable hyperbolic metamaterials, quantum computing, and thermionic‐emission‐based thermoelectric and thermophotonic energy conversion devices.

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Hollow Plasmonic P‐Metal‐N S‐Scheme Heterojunction Photoreactor with Spatially Separated Dual Cocatalysts toward Artificial Photosynthesis

Zhang,

Shi,

Zhao

et al. 2023

Small

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Semiconductor‐based step‐scheme (S‐scheme) heterojunctions possess many merits toward mimicking natural photosynthesis. However, their applications for solar‐to‐chemical energy conversion are hindered by inefficient charge utilization and unsatisfactory surface reactivity. Herein, two synergistic protocols are demonstrated to overcome these limitations based on the construction of a hollow plasmonic p‐metal‐n S‐scheme heterojunction photoreactor with spatially separated dual noble‐metal‐free cocatalysts. On one side, plasmonic Au, inserted into the heterointerfaces of CuS@ZnIn2S4 core–shell nanoboxes, not only accelerates the transfer and recombination of useless charges, enabling a more thorough separation of useful ones for CO2 reduction and H2O oxidation but also generates hot electrons and holes, respectively injects them into ZnIn2S4 and CuS, further increasing the number of active carriers participating in redox reactions. On the other side, Fe(OH)x and Ti3C2 cocatalysts, separately located on the CuS and ZnIn2S4 surface, enrich the redox sites, adjust the reduction potential and pathway for selective CO2‐to‐CH4 transformation, and balance the transfer and consumption of photocarriers. As expected, significantly enhanced activity and selectivity in CH4 production are achieved by the smart design along with nearly stoichiometric ratios of reduction and oxidation products. This study paves the way for optimizing artificial photosynthetic systems via rational interfacial channel introduction and surface cocatalyst modification.

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Simultaneous harnessing of hot electrons and hot holes achieved via n-metal-p Janus plasmonic heteronanocrystals

Cited by 33 publications

References 65 publications

Construction of Plasmonic Metal@Semiconductor Core–Shell Photocatalysts: From Epitaxial to Nonepitaxial Strategies

Construction of Plasmonic Metal@Semiconductor Core–Shell Photocatalysts: From Epitaxial to Nonepitaxial Strategies

Thermionic Emission in Artificially Structured Single‐Crystalline Elemental Metal/Compound Semiconductor Superlattices

Hollow Plasmonic P‐Metal‐N S‐Scheme Heterojunction Photoreactor with Spatially Separated Dual Cocatalysts toward Artificial Photosynthesis

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